【摘要】 <正> 我们曾报道1,10-N,N’-双取代-1,10-二氮-4,7,13,16-四氧环十八烷(1)及1,7-N,N’-双取代-1,7-二氮-4,10-二氧环十二烷(2)二类大环聚醚的合成及其对碱金属离子的络合性能。更多还原

【Abstract】 In present paper we describe the method of preparation of 1,7-disubstituted,1,7-diaza-4,10,13-trioxacyclopentadecane (3a—d),where the substitution group is d (?) 1. The synthesis of 3a-d1) Synthesis of the side chains (?) see scheme 2 in previous paper.2) Synthesis of the mother ring 1,7-diaza-4,10,13-trioxacyclopentadecane (abbre-viated as [2.1]) was achieved by condensation of the sodium salt of N,N’-ditosyl 1,2(2-aminoethoxy)ethane with diethylene glycol ditosylate,and reduction of the cyclizationproduct in liquid ammonia (Scheme 2). 2. The synthesis of the N,N’-disubstituted [2.1] Four ligands were prepared according to the scheme 3.The purification of the finalproducts was achieved by same procedure described in previous paper except that the highvacuum distillation step was omitted,and the residue after removal of chloroform wasfurther extracted by heptane.The improved method gave higher purity and yields of finalproducts (yields>50%). 3. The characteristics of the mass spectra of macrocyclic polyethers The scheme 4 indicates the pattern of the bond fission in mass spectrum process,and Table 2 shows the distribution and the relative strength of various ions formed inmass spectrum condition.Obviously,the rupture of bonds are not in random:the N—Cbonds are more stable than C—O and C—C bonds;the bonds between C_α and C_β of Cα-C_β-X(X=O or N)are liable to fission;and the side chains are less stable than the bondsexisted in mother ring.By using this regularity of susceptibility toward fission of variousbonds,the mass spectrum method may be used to identify the purity of the macrocyclopo-lyethers.The reaction intermediates such as the ligands of monosubstituted side chain arethe impurities found in final products.A small amount of this impurities could not beidentified by NMR but in the case of mass spectrum analysis,the peaks of these impuritiesare clearly observed,and the completeness of the reaction can be judged by this technique.更多还原